US1734050A - Manufacture of sulphonated oils, fats, fatty acids, and waxes - Google Patents
Manufacture of sulphonated oils, fats, fatty acids, and waxes Download PDFInfo
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- US1734050A US1734050A US251737A US25173728A US1734050A US 1734050 A US1734050 A US 1734050A US 251737 A US251737 A US 251737A US 25173728 A US25173728 A US 25173728A US 1734050 A US1734050 A US 1734050A
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- Prior art keywords
- oil
- sulphonation
- oils
- bleaching
- acid
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- 239000003921 oil Substances 0.000 title description 54
- 235000014113 dietary fatty acids Nutrition 0.000 title description 21
- 239000000194 fatty acid Substances 0.000 title description 21
- 229930195729 fatty acid Natural products 0.000 title description 21
- 239000003925 fat Substances 0.000 title description 20
- 150000004665 fatty acids Chemical class 0.000 title description 20
- 239000001993 wax Substances 0.000 title description 17
- 238000004519 manufacturing process Methods 0.000 title description 15
- 235000019198 oils Nutrition 0.000 description 52
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 23
- 239000007844 bleaching agent Substances 0.000 description 20
- 235000019197 fats Nutrition 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 239000002253 acid Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 238000004061 bleaching Methods 0.000 description 17
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000001117 sulphuric acid Substances 0.000 description 8
- 235000011149 sulphuric acid Nutrition 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000011282 treatment Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000004359 castor oil Substances 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000014593 oils and fats Nutrition 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 239000004159 Potassium persulphate Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 for example Substances 0.000 description 2
- 239000012182 japan wax Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000009896 oxidative bleaching Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000009895 reductive bleaching Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical class C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 229910000286 fullers earth Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000010491 poppyseed oil Substances 0.000 description 1
- 239000010499 rapseed oil Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- LUPNKHXLFSSUGS-UHFFFAOYSA-M sodium;2,2-dichloroacetate Chemical compound [Na+].[O-]C(=O)C(Cl)Cl LUPNKHXLFSSUGS-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
Definitions
- the sulphonation' process is further not limited to natural oils and fats containing mono-basic fatty acids and to the mono-basic fatty acids themselves but can also be extended to polybasic acids, such as mucic,
- adipic, subericorthe like acids and to oils and fats containing these acids, whether such oils, fats and fatty acids occur in nature as such or are synthetically prepared.
- the process is also adapted to numerous substances existing in the large domain of the waxes, for example, japan wax, beeswax, carnauba wax, as well as Montan wax, ceresine and the like. In this case also not only the naturally obtained, but also the synthetically prepared products, can be employed.
- The' expression sulphonation is to be under-' stood to include, "besides the action of 5111- phuric acid, treatment of the oils, fats and the like with organic sulpho-acids withor without the addition of sulphuric acid.
- the organic sulpho-acids employed for this purpose may be either aliphatic or aromat c; of the latter B-naphthalenesulphomc acid and its homologues, as Well as the derivatives of these homologues obtained by the addition of alkyl and aryl side chains, are especially suitable.
- the sulphonation can further be effected tionwith substances capable of evolving sulphurous acid. In this case it is usually necessary also to subject the oils etc. to oxidation. This oxidation can be effected after the completion of the sulphurous acid action gr at the same time asthe latter. In both cases the oils etc.
- sulphonation may be bleached simultaneously with the sulphonation, either by the reducing ac-v tion of the sulphurous acid or by adding a suitable quantity of the oxidizing agent, so that the adition of a special bleaching agent can, under certain circumstances, be dispensed with. It is also possible by this sulphonation process to convert into sulpho-compounds such oils, fats, fatty acids, waxes etc. as, for example, mineral oils of the aliphatic group, which ofi'er considerable difficulties to a conversion of this kind.
- an already bleached oil and, on the other hand, by an after-bleaching of the finished product.
- the after-bleaching can be effected either directly after the completion of the reaction, whilst the reaction mixture is still acid, or after the subsequent neutralization of the oil.
- oxidizing bleaching agents hydrogen peroxide, as well as all the peroxides and all such substances as are capable of giving off active oxygen in acid solution, especially percompounds such as per-sulpho acids, alkali persulphates, alkali percarbonates. alkali perborates, peroxides of organic acids (such as acetyl peroxide and benzoyl peroxide) compounds of hydrogen peroxide with organic bodies such as benzoic acid and urea, can be used.
- hypochlorites that are unstable in the presence of acids may also be used.
- Example 1 i 100 kgms. of the palest castor oil, previous- 1y bleached if desired, are sulphonated with 18 kgms. of concentrated sulphuric acid (96 98%) for about four hours. During the sulphonation 16 kgms. of hydrogen peroxide (30%) are added in portions of 4 kgms. at a time. The reaction temperature should. be
- the acid oil is prepared as above except that only 12 kgms. of hydrogen peroxide are used instead of 16 kgms.
- the pale yellow product obtained after the neutralization is subjected to an after-bleaching by being treated for half an hour at about 60 (lwith 2% l-Igms. of alkali hydrosulphite, with con: tinual stirring.
- hydrosulphite one of the oxidizing agents mentioned,-for example, a suitable quantity of sodium, potassium, or calcium hypochlorite-can be employed in the after-bleaching operation.
- Example 3 This is the same as Example 1 except that a suitable quantity of sodium, potassium or ammonium persulphate or percarbonate or perborate is employed instead of hydrogen peroxide; otherwise the process is the same as Example 1.
- a suitable quantity of sodium, potassium or ammonium persulphate or percarbonate or perborate is employed instead of hydrogen peroxide; otherwise the process is the same as Example 1.
- percarbonate or perborate the quantity of sulphuric acid must be suitably increased on account of its decomposition with these salts.
- E mample 4 100 kgms. of the palest castor oil, previously bleached if desired, are sulphonated with 18 kgms. of concentrated sulphuric acid (9698%) for about four hours. During the sulphonation 9 kgms. of 30% hydrogen peroxide are added in portions and, after sulphonation has been effected, a quantity of sodium, potassium, or ammonium persulphate or percarbonate, or of a mixture of, these bodies, corresponding to the remaining 7 kgms. of hydrogen peroxide, is added. The reverse process may also be employed-i.
- the persulphate, pcrcarbonate or perborate may be added during the sulphonation in a quantity corresponding to active oxygen in 9 kgms. of hydrogen peroxide, and 7 kgms. of hydrogen peroxide added after the sulphonation,
- Example 5 100 kgms. of oil are treated with 12 kgms. of 30% hydrogen peroxide or with .a corresponding quantity of sodium, potassium or amonium persulphate, percarbonate, or perborate, or mixtures of these bodies, and thereupon, after the sulphonation, 2 kgms. of alkali hydrosulphite or of a compound of formaldehyde with alkali hydrosulphite or alkali sulphoxylate are added to the acid or partially neutralized oil.
- the quantity of sulphuric acid must be suitably increased when per-carbonates or perborates are used.
- the excess of acid is preferably neutralized.
- This can be efiected by simply washing the oils with water or by adding neutralizing agents such as soda to the fresh sulphonation mixture and washing out the resulting salts or by washing the neutralized oils with suit- 'able organic solvents such as alcohol, ether or the like.
- the oils can also be used with a definite content of free acidi. e., without being neutralized.
- any of the other oils, fats, fatty acids, and Waxes hereinbefore mentioned can be employed.
- Other sulphonation methods can also be employed.
- Example 6' 109 kgms. of preliminarily bleached palm oil are sulphonated with 18 kgms. of concentrated sulphuric acid (96-98%) for about four hours. During the sulphonation l6 kgms. hydrogen peroxide are added in four portions of 4 kgms. at a time. The reaction temperature is to be kept at about 40 to C. After sulphonation the oil is further worked up in known manner.
- Example 7 I The preparation of the acid oil "is carried out as above, but instead of sulphuric acid the same quantity of sulphanilic acid is used together with a suitable catalyst. The further treatment is the same as in the above described example.
- Example 8 100 kgms. of a pale japan wax are melted at moderate temperature and are sulphonated with 16 kgms. of sulphanilic acid together with a suitable catalyst, the above described quantity of hydrogen peroxide being added. The further treatment follows in the usual manner, after the neutralization, however, the product is treated by the addition of suitable reagents to render the sulphonated wax liquid at the ordinary temperature.
- the process further offers the particular advantage that, owing to the presence of bleaching agents in the sulphonation process, a larger number of sulpho groups is taken up by the fats, oils, etc., treated.
- the oils obtained by this process are consequently distinguished by a greater stability towards limeand salt-containing water, as well as towards acid reacting water etc. used in sub sequent treatments.
- the products obtained in thisway also possess an'outstanding softening property.
- My invention is intended to be utilized for sulphonating oils and fats of animal and plant origin.
- oil any oil which refers to oil
- I an 'oil or fat or fatty acid of animal or plant origin.
- the improved process produces a new product, namely, a sulphonated and oxidized oil which is stable towards lime/ and magnesia.
- lVhat I claim is zl.
- a "process for preparing from an oil, fat, fatty acid, or wax, a substantially decolorized sulphonated product consisting of subjecting said substance to sulphonation in the presence of a bleaching agent assisting said sulphonation and employed in excess of the quantity required for assisting said sulphonation.
- fat, fatty acid, or wax a substantially decolorized sulphonated product, consisting of subjecting said substance to a preliminary bleaching operation, thento sulphonation in the presence of a bleaching agent, and then to an after-bleaching operation.
- fat, fatty acid, or wax a substantially decolorized sulphonated product, consisting of subjecting said substance to sulphonation in the presence of a bleaching agent and then to an after-bleaching by a physically acting bleaching agent.
- a process for preparing from an oil, fat, fatty acid, or wax asubstantially decoloi'ized sulphonated product consisting of subjecting said substance to a preliminary bleaching by a physically acting bleaching agent, then to sulphonation in the presence of a bleaching agent, and then to an afterblcacliing by a physically acting bleaching agent.
- a process for preparing from an oil, fat, fattyacid, or wax a substantially decolorized sulphonated product consisting of subjectin said substance to sulphonation in the presence of a bleaching agent, ncutralizing the said sulphonated substance, and then subjecting said ncutralizedsubstance to an after-bleaching operation.
- a process for preparing from an oil, fat, fatty acid, or wax a substantially decolorized sulphonated product consisting of subjecting said substance to sulphonation in the presence of a bleaching agent and to an atter-blcaching operation and then neutralizing said bleached and sulphonated substance.
- a process for preparing from an oil, fat, fatty acid, or Wax a substantially decolorized sulph'onatcd product consisting of subjecting -said substance to sulphonation by an organic sulpho-acid in the presence of a bleaching agent.
- a process for preparing from an oil, fat, fatty acid, or Wax a substantially decolorizeil sulphonated product consisting of subjecting said substance to sulphonation by an organic sulp'ho-acid in the presence of sulphuric acid and a bleaching agent.
- a substantially decolorized bleached sulphonated oil 14.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Fats And Perfumes (AREA)
Description
' Patented N W. 5, 1929 orrc WILLY SECK, or aucsnune, GERMANY, ASSIGNOR '1'0 ERIBA AKrIENGEsELLscnAFr,
or zuarcn, SWITZERLAND MANUFACTURE OF SULPHONATED OILS, FATS,- FATTY ACIDS, AND WAXES No Drawing. Application filed. February 3, 1928, Serial No. 251,737, and in Germany July 28, 1927.
Sulphonated oils-i. e., the commercial products designated by the general term Turkey red oil and preparations similar to Turkey red oil'are employed for widely differing purposes of the industries working with these products (textile industry, leather industry etc.). I
It has now been found, that very many naturally occurring mineral, animal and vegetable fats, oils,'fatty acids and waxes can be converted into sulpho-compounds by the process hereinafter described. Castor oil, linseed oil, rape oil, palm oil and poppy-seed oil, serve as-examples. Further all oils which have undergone treatment, for example, the
blown and boiled oils shown in the manufacture of lineseed-oil'and varnish, as well'as hydrogenated fats and oils can also be subjected to this process. In all these cases the corresponding fatty acids themselves can also be subjected to the sulphonation process.
The sulphonation' process is further not limited to natural oils and fats containing mono-basic fatty acids and to the mono-basic fatty acids themselves but can also be extended to polybasic acids, such as mucic,
adipic, subericorthe like acids, and to oils and fats containing these acids, whether such oils, fats and fatty acids occur in nature as such or are synthetically prepared.
The process is also adapted to numerous substances existing in the large domain of the waxes, for example, japan wax, beeswax, carnauba wax, as well as Montan wax, ceresine and the like. In this case also not only the naturally obtained, but also the synthetically prepared products, can be employed.
The' expression sulphonation is to be under-' stood to include, "besides the action of 5111- phuric acid, treatment of the oils, fats and the like with organic sulpho-acids withor without the addition of sulphuric acid.
. The organic sulpho-acids employed for this purpose may be either aliphatic or aromat c; of the latter B-naphthalenesulphomc acid and its homologues, as Well as the derivatives of these homologues obtained by the addition of alkyl and aryl side chains, are especially suitable. v 4 The sulphonation can further be effected tionwith substances capable of evolving sulphurous acid. In this case it is usually necessary also to subject the oils etc. to oxidation. This oxidation can be effected after the completion of the sulphurous acid action gr at the same time asthe latter. In both cases the oils etc. may be bleached simultaneously with the sulphonation, either by the reducing ac-v tion of the sulphurous acid or by adding a suitable quantity of the oxidizing agent, so that the adition of a special bleaching agent can, under certain circumstances, be dispensed with. It is also possible by this sulphonation process to convert into sulpho-compounds such oils, fats, fatty acids, waxes etc. as, for example, mineral oils of the aliphatic group, which ofi'er considerable difficulties to a conversion of this kind.
The applicability of sulphonated oils of this kind to the widely differing purposes of the industries working with such preparations has hitherto been to a certain extent limited by the colour perculiar to these products. Thus, for example, when using Turkey red oils, finishing oils and like means inthe finishing of white goods, one had always to reckon with an often not inconsiderable spoiling of the whitness of the goods. Similar phenomena were observed in the working up of leather. I Y
It has hitherto not been technically possible to subject Turkey red oils and preparations similar to Turkey red oil to a bleaching process. Furthermore it could not have been foretold whether a preparation of such colourless products could be effected at all, since by sulphonating it might have been just as pos-- sible to give the body obtained a characteristic colour which, as a typical optical property, is inseparably bound with the other known properties of Turkey red oil (i. e. stability in the presence of salts, lime and acid, softeningproperties etc.) L
It has nowbeen unexpectedly discovered ,phonation or after neutralization bleaching that colourless Turkey red oils and preparations similar to Turkey red oil can be Very readily obtained without detriment to the typical Turkey red oil properties of these products. According to the present process, the manufacture of the oil is carried out in the presence of oxidizing or'reducing bleaching agents. When oxidizing bleaching agents are used, these also influence the sulphonation process. On this account such quantities of the oxidizing substances are employed that,
as well as influencing the sulphonation they also effect the bleaching action. The etl'ect is assisted by, on the one hand, sulphonating.
an already bleached oil and, on the other hand, by an after-bleaching of the finished product. The after-bleaching can be effected either directly after the completion of the reaction, whilst the reaction mixture is still acid, or after the subsequent neutralization of the oil.
For the last mentioned preliminary and after-bleaching there may be used, besides the oxidizing or reducing substances, bleaching agents whose bleaching action depends preferably on absorption or adsorption phenomena, unconnected with purely chemical action (fullers earth, etc.)
As oxidizing bleaching agents hydrogen peroxide, as well as all the peroxides and all such substances as are capable of giving off active oxygen in acid solution, especially percompounds such as per-sulpho acids, alkali persulphates, alkali percarbonates. alkali perborates, peroxides of organic acids (such as acetyl peroxide and benzoyl peroxide) compounds of hydrogen peroxide with organic bodies such as benzoic acid and urea, can be used.
For the bleaching process before sulagentse. g. hypochloritesthat are unstable in the presence of acids may also be used.
The following reducing bleaching agents,
Example 1 i 100 kgms. of the palest castor oil, previous- 1y bleached if desired, are sulphonated with 18 kgms. of concentrated sulphuric acid (96 98%) for about four hours. During the sulphonation 16 kgms. of hydrogen peroxide (30%) are added in portions of 4 kgms. at a time. The reaction temperature should. be
about 4050 C. Deviations from this temperature have no great effect. After sulphonation the oil is further treated in the known manner.
li'wample 2 The acid oil is prepared as above except that only 12 kgms. of hydrogen peroxide are used instead of 16 kgms. The pale yellow product obtained after the neutralization is subjected to an after-bleaching by being treated for half an hour at about 60 (lwith 2% l-Igms. of alkali hydrosulphite, with con: tinual stirring. Instead of hydrosulphite one of the oxidizing agents mentioned,-for example, a suitable quantity of sodium, potassium, or calcium hypochlorite-can be employed in the after-bleaching operation.
Example 3 This is the same as Example 1 except that a suitable quantity of sodium, potassium or ammonium persulphate or percarbonate or perborate is employed instead of hydrogen peroxide; otherwise the process is the same as Example 1. When using percarbonate or perborate the quantity of sulphuric acid must be suitably increased on account of its decomposition with these salts.
E mample 4 100 kgms. of the palest castor oil, previously bleached if desired, are sulphonated with 18 kgms. of concentrated sulphuric acid (9698%) for about four hours. During the sulphonation 9 kgms. of 30% hydrogen peroxide are added in portions and, after sulphonation has been effected, a quantity of sodium, potassium, or ammonium persulphate or percarbonate, or of a mixture of, these bodies, corresponding to the remaining 7 kgms. of hydrogen peroxide, is added. The reverse process may also be employed-i. e., the persulphate, pcrcarbonate or perborate may be added during the sulphonation in a quantity corresponding to active oxygen in 9 kgms. of hydrogen peroxide, and 7 kgms. of hydrogen peroxide added after the sulphonation,
Example 5 100 kgms. of oil are treated with 12 kgms. of 30% hydrogen peroxide or with .a corresponding quantity of sodium, potassium or amonium persulphate, percarbonate, or perborate, or mixtures of these bodies, and thereupon, after the sulphonation, 2 kgms. of alkali hydrosulphite or of a compound of formaldehyde with alkali hydrosulphite or alkali sulphoxylate are added to the acid or partially neutralized oil. In this case also as in Example 3 the quantity of sulphuric acid must be suitably increased when per-carbonates or perborates are used.
In all cases, after the sulphonation is comarsaoso plete, the excess of acid is preferably neutralized. This can be efiected by simply washing the oils with water or by adding neutralizing agents such as soda to the fresh sulphonation mixture and washing out the resulting salts or by washing the neutralized oils with suit- 'able organic solvents such as alcohol, ether or the like.- For certain special purposes, however, the oils can also be used with a definite content of free acidi. e., without being neutralized. I
In place of the castor oil mentioned in the examples any of the other oils, fats, fatty acids, and Waxes hereinbefore mentioned can be employed. Other sulphonation methods can also be employed.
Example 6' 109 kgms. of preliminarily bleached palm oil are sulphonated with 18 kgms. of concentrated sulphuric acid (96-98%) for about four hours. During the sulphonation l6 kgms. hydrogen peroxide are added in four portions of 4 kgms. at a time. The reaction temperature is to be kept at about 40 to C. After sulphonation the oil is further worked up in known manner.
Example 7 I The preparation of the acid oil "is carried out as above, but instead of sulphuric acid the same quantity of sulphanilic acid is used together with a suitable catalyst. The further treatment is the same as in the above described example.
Example 8 100 kgms. of a pale japan wax are melted at moderate temperature and are sulphonated with 16 kgms. of sulphanilic acid together with a suitable catalyst, the above described quantity of hydrogen peroxide being added. The further treatment follows in the usual manner, after the neutralization, however, the product is treated by the addition of suitable reagents to render the sulphonated wax liquid at the ordinary temperature.
The production of colourless Turkey .red oil preparations which, on the one hand possess the typical properties of hitherto nown products, and on the other hand, in
' contradistinction to these products, exhibit no partial absorption of light and are thus colourless provides a not unimportant technical advance and renders it possible to use such products to a much more unlimited extent that has beenhitherto possible.
The process further offers the particular advantage that, owing to the presence of bleaching agents in the sulphonation process, a larger number of sulpho groups is taken up by the fats, oils, etc., treated. The oils obtained by this process are consequently distinguished by a greater stability towards limeand salt-containing water, as well as towards acid reacting water etc. used in sub sequent treatments. Finally the products obtained in thisway also possess an'outstanding softening property.
My invention is intended to be utilized for sulphonating oils and fats of animal and plant origin. Hence whenever I refer to oil,"it is undei stood that I refer to an 'oil or fat or fatty acid of animal or plant origin. The improved process produces a new product, namely, a sulphonated and oxidized oil which is stable towards lime/ and magnesia.
The claim for the product is not to be re stricted to the specific process above mentioned.
lVhat I claim is zl. A process for preparing from an oil, fat, fatty acid, or wax, a substantially decolorized sulphonated product, consisting of subjecting said substance to sulphonation in the presence of a bleaching agent.-
2. A "process for preparing from an oil, fat, fatty acid, or wax, a substantially decolorized sulphonated product, consisting of subjecting said substance to sulphonation in the presence of a bleaching agent assisting said sulphonation and employed in excess of the quantity required for assisting said sulphonation.
3. A process for preparing'from an oil,
fat, fatty acid, or wax a substantially decol- 6. A process for preparing from an oil,-
fat, fatty acid, or waxa substantially decolorized sulphonated product, consisting of subjecting said substance to a preliminary bleaching operation, thento sulphonation in the presence of a bleaching agent, and then to an after-bleaching operation.
7.-A process for preparing. from an oil,
fat, fatty acid, or wax a substantially decolorized sulphonated product, consisting of subjecting said substance to a preliminary bleaching by a physically acting bleaching I 1 agent and then to sulphonation in the presence of a bleaching agent. 8. A process for preparingv from an oil,
fat, fatty acid, or wax a substantially decolorized sulphonated product, consisting of subjecting said substance to sulphonation in the presence of a bleaching agent and then to an after-bleaching by a physically acting bleaching agent. 1
9. A process for preparing from an oil, fat, fatty acid, or wax asubstantially decoloi'ized sulphonated product, consisting of subjecting said substance to a preliminary bleaching by a physically acting bleaching agent, then to sulphonation in the presence of a bleaching agent, and then to an afterblcacliing by a physically acting bleaching agent.
10. A process for preparing from an oil, fat, fattyacid, or wax a substantially decolorized sulphonated product, consisting of subjectin said substance to sulphonation in the presence of a bleaching agent, ncutralizing the said sulphonated substance, and then subjecting said ncutralizedsubstance to an after-bleaching operation.
11. A process for preparing from an oil, fat, fatty acid, or wax a substantially decolorized sulphonated product, consisting of subjecting said substance to sulphonation in the presence of a bleaching agent and to an atter-blcaching operation and then neutralizing said bleached and sulphonated substance.
12. A process for preparing from an oil, fat, fatty acid, or Wax a substantially decolorized sulph'onatcd product, consisting of subjecting -said substance to sulphonation by an organic sulpho-acid in the presence of a bleaching agent.
13. A process for preparing from an oil, fat, fatty acid, or Wax a substantially decolorizeil sulphonated product, consisting of subjecting said substance to sulphonation by an organic sulp'ho-acid in the presence of sulphuric acid and a bleaching agent.
14. A substantially decolorized bleached sulphonated oil.
I In testimony whereof I hereunto afiix my signature.
WILLY SEGK.
Applications Claiming Priority (1)
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DE1734050X | 1927-07-28 |
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US1734050A true US1734050A (en) | 1929-11-05 |
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US251737A Expired - Lifetime US1734050A (en) | 1927-07-28 | 1928-02-03 | Manufacture of sulphonated oils, fats, fatty acids, and waxes |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2486373A (en) * | 1946-12-11 | 1949-11-01 | Sonneborn Sons Inc L | Heat stabilization of petroleum mahogany sulfonates |
US2693487A (en) * | 1948-01-30 | 1954-11-02 | Monsanto Chemicals | Monosulfonation of benzene |
US2846457A (en) * | 1953-09-28 | 1958-08-05 | Rayette Inc | Decolorized detergents and method of manufacture |
US2851483A (en) * | 1954-10-20 | 1958-09-09 | Sonneborn Sons Inc L | Bleached mahogany sulfonic compounds |
US2999871A (en) * | 1959-12-01 | 1961-09-12 | Gen Aniline & Film Corp | Process of improving the odor of sulfoalkyl esters of fatty acids |
US3142691A (en) * | 1962-02-02 | 1964-07-28 | Henkel & Cie Gmbh | Production of light-colored sulfonated fatty acids and fatty acid derivatives |
US3159657A (en) * | 1961-05-19 | 1964-12-01 | Henkel & Cie Gmbh | Preparation of light-colored sulfonated fatty acids and fatty acid derivatives |
US3354187A (en) * | 1962-03-09 | 1967-11-21 | Henkel & Cie Gmbh | Bleaching dark-colored sulfonation products |
-
1928
- 1928-02-03 US US251737A patent/US1734050A/en not_active Expired - Lifetime
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2486373A (en) * | 1946-12-11 | 1949-11-01 | Sonneborn Sons Inc L | Heat stabilization of petroleum mahogany sulfonates |
US2693487A (en) * | 1948-01-30 | 1954-11-02 | Monsanto Chemicals | Monosulfonation of benzene |
US2846457A (en) * | 1953-09-28 | 1958-08-05 | Rayette Inc | Decolorized detergents and method of manufacture |
US2851483A (en) * | 1954-10-20 | 1958-09-09 | Sonneborn Sons Inc L | Bleached mahogany sulfonic compounds |
US2999871A (en) * | 1959-12-01 | 1961-09-12 | Gen Aniline & Film Corp | Process of improving the odor of sulfoalkyl esters of fatty acids |
US3159657A (en) * | 1961-05-19 | 1964-12-01 | Henkel & Cie Gmbh | Preparation of light-colored sulfonated fatty acids and fatty acid derivatives |
US3142691A (en) * | 1962-02-02 | 1964-07-28 | Henkel & Cie Gmbh | Production of light-colored sulfonated fatty acids and fatty acid derivatives |
US3354187A (en) * | 1962-03-09 | 1967-11-21 | Henkel & Cie Gmbh | Bleaching dark-colored sulfonation products |
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